We study fluctuation theorems for open quantum systems with a non-Markovian heat bath using the approach of quantum master equations and examine the physical quantities that appear in those fluctuation theorems. The approach of Markovian quantum master equations to the fluctuation theorems was developed by Esposito and Mukamel [Phys. Rev. E {\bf73}, 046129 (2006)]. We show that their discussion can be formally generalized to the case of a non-Markovian heat bath when the local system is linearly connected to a Gaussian heat bath with the spectrum distribution of the Drude form. We found by numerically simulating the spin-boson model in non-Markovian regime that the detailed balance condition is well satisfied except in a strongly non-equilibrium transient situation, and hence our generalization of the definition of the entropy production is almost always legitimate. Therefore, our generalization of the fluctuation theorem seems meaningful in wide regions.
We study fluctuation theorems for open quantum systems with a non-Markovian heat bath using the approach of quantum master equations and examine the physical quantities that appear in those fluctuation theorems. The approach of Markovian quantum master equations to the fluctuation theorems was developed by Esposito and Mukamel [Phys. Rev. E {\bf73}, 046129 (2006)]. We show that their discussion can be formally generalized to the case of a non-Markovian heat bath when the local system is linearly connected to a Gaussian heat bath with the spectrum distribution of the Drude form. We found by numerically simulating the spin-boson model in non-Markovian regime that the detailed balance condition is well satisfied except in a strongly non-equilibrium transient situation, and hence our generalization of the definition of the entropy production is almost always legitimate. Therefore, our generalization of the fluctuation theorem seems meaningful in wide regions.
We study fluctuation theorems for open quantum systems with a non-Markovian heat bath using the approach of quantum master equations and examine the physical quantities that appear in those fluctuation theorems. The approach of Markovian quantum master equations to the fluctuation theorems was developed by Esposito and Mukamel [Phys. Rev. E 73, 046129 (2006)]. We show that their discussion can be formally generalized to the case of a non-Markovian heat bath when the local system is linearly connected to a Gaussian heat bath with the spectrum distribution of the Drude form. We found by numerically simulating the spin-boson model in non-Markovian regime that the "detailed balance" condition is well satisfied except in a strongly nonequilibrium transient situation, and hence our generalization of the definition of the "entropy production" is almost always legitimate. Therefore, our generalization of the fluctuation theorem seems meaningful in wide regions.
We study fluctuation theorems for open quantum systems using the approach of quantum master equations, and examine the thermodynamic quantities that appear in those fluctuation theorems. The approach of Markovian quantum master equations to the fluctuation theorems was developed by Esposito and Mukamel [Phys. Rev. E 73, 046129 (2006)]. We show that their discussion can be formally generalized to the case of a non-Markovian heat bath in the case where the local system is linearly connected to the Gaussian heat bath with the spectrum distribution of the Drude form. However, we found that the thermodynamic quantities that appear in those fluctuation theorems can be ill-defined or inconsistent with each other by numerically simulating the spin-boson model.
We present a general quantum fluctuation theorem for the entropy production of an open quantum system coupled to multiple environments, not necessarily at equilibrium. Such a general theorem, when restricted to the weak-coupling and Markovian regime, holds for both local and global master equations, corroborating the thermodynamic consistency of local quantum master equations. The theorem is genuinely quantum, as it can be expressed in terms of conservation of a Hermitian operator, describing the dynamics of the system state operator and of the entropy change in the baths. The integral fluctuation theorem follows from the properties of such an operator. Furthermore, it is also valid when the system is described by a time-dependent Hamiltonian. As such, the quantum Jarzynski equality is a particular case of the general result presented here. Moreover, our result can be extended to nonthermal baths, as long as microreversibility is preserved. We present some numerical examples to showcase the exact results previously obtained. We finally generalize the fluctuation theorem to the case where the interaction between the system and the bath is explicitly taken into account. We show that the fluctuation theorem amounts to a relation between time-reversed dynamics of the global density matrix and a two-time correlation function along the forward dynamics involving the baths' entropy alone.
A consistent theory of non-equilibrium thermodynamics for Markovian open quantum systems has been developed in the late seventies in analogy with Classical Irreversible Thermodynamics. The time-evolution of these open systems is usually described by means of effective master equations in Lindblad form, that turn out to be reliable when there is a separation of time-scales between system and environment, such that memory effects are negligible and the so-called Markovian approximation is justified. In this framework, the variations of energy and entropy in the system are consistently described, distinguishing between heat and work contributions and providing a statement of the second law of thermodynamics as positivity of the entropy production.\nHowever, there is empirical evidence that many physical systems like photosynthetic complexes,\nopto-mechanical resonators and superconducting qubits, just to mention a few, experience more general non-Markovian dynamics. The formulation of the laws of thermodynamics in a non-Markovian setting is matter of current research and represents the main topic of the present work. As a first step, we show that the entropy production defined as in the Markovian case can be negative for a class of non-Markovian dynamics. We argue that this outcome should not be interpreted as a violation of the second law of thermodynamics because the environment must be explicitly taken into account in the balance of entropy in the non-Markovian setting. In order to justify this claim we adopt a more general point of view, studying a closed bipartite quantum system, such that each of the two subsystems plays the role of a finite environment out of equilibrium for the other one. We concentrate on the balance of energy first and construct an effective Hamiltonian for each subsystem using physically reasonable requirements; then we define heat and work as in the standard Markovian treatment, with the effective Hamiltonian replacing the free Hamiltonian. It turns out that, in our framework, the work power is perfectly balanced between subsystems, while the correlations can store a part of energy locally inaccessible and exchange it with both subsystems in the form of heat.\nConcerning the balance of entropy, a quite general formulation of the second law of thermodynamics can be given as follows: under the assumption of a factorized initial state for the compound system, the sum of the total variations of the entropies in the two subsystems is always nonnegative. We show with an explicit example that this general formulation does not correspond to the statement presented in the framework of Markovian master equations, which should not be considered a priori the second law of thermodynamics.\nIn the last part of the thesis we concentrate of the so-called fluctuation relations, that are results extending the thermodynamic formalism beyond the behavior of average quantities. After reviewing the main theoretical outcomes, such as the Jarzynski equality and the Crooks fluctuation theorem, we describe a proposal to access experimentally the work performed on an ensemble of diatomic molecules by a time-dependent electric field coupled with their vibrational degree of freedom. This procedure could then be used to test the quantum Jarzynski equality. With respect to the results so far appeared in the literature, in which the left-hand side of the equality is inferred from an experiment and the right-hand side is computed according to a model, in our proposed setting we should be able to estimate from the experiment both the left-hand side and the right-hand side of the equality, independently.
The quantum exchange fluctuation theorem relates the probabilities of observing heat transfer along and against the temperature gradient between thermal baths at different temperatures. We investigate how this relation generalizes when the baths exhibit non-Markovian dynamics. Using a microscopic collisional model, bath memory is generated through interactions between successive bath auxiliaries before each heat-exchange collision. We derive exchange fluctuation theorems for both direct bath-bath interactions and probe-mediated heat exchange in the steady-state regime. As an illustrative example, we consider heat baths with qubit auxiliaries and show that non-Markovian memory enhances the probability of heat-transfer events against the temperature gradient, modifying the predictions made by the conventional Jarzynski-Wójcik exchange fluctuation theorem. Our results establish a microscopic connection between environmental memory and non-equilibrium heat-exchange statistics.
Markovian quantum master equations (MQMEs) were established nearly half a century ago. They have often been used in the study of irreversible thermodynamics. However, the previous results were mainly concerned about ensemble averages; the stochastic thermodynamics of these systems went unnoticed for a very long time. This situation remained unchanged until a variety of fluctuation theorems in classical and quantum regimes were found in the past two decades. In this paper, we systematically summarize the current understanding on the stochastic heat and work in MQMEs using two distinct strategies. One strategy is to treat the system and its surrounding heat bath as a closed quantum system, to suppose that the evolution of the composite system is unitary under a time-dependent total Hamiltonian and to define the heat and work as the changes in energy by applying two energy measurements scheme to the composite system. The other strategy is to unravel these MQMEs into random quantum jump trajectories (QJTs) and to define the stochastic heat and work along the individual trajectories. Many important physical concepts, mathematical techniques, and fluctuation theorems at different descriptive levels are given in as detailed a manner as possible. We also use concrete models to illustrate these results.